Azo lake and process of making same.



UNlE srarns Parana:

ERNST ULRIOHS, OF ELBERFELD, GERMANY, ASSIGNOR 'lO 'llllfi l- [RM 01"\YlllLi'lNG, DAllL & CO., AOTIENGESELLSCHAFT, ()l" BARMI'IN, GERMANY.

.AZO LAKE AND PROCESS OF MAKING SAME.

Application filed September 4, 1907. Serial No. 391,35

To all whom it may concern:

Be it known that I, ERNST ULRIGHS, a subject of the King of Prussia,German Eur peror, and resident of Elberfeld, Province of the Rhine,German Empire, have invented new and useful Improvements in theMannfacture of A20 Lakes, of which the following is an exactspecification.

Lakes from azo-colors are at present manufactured, as is well known, insuch manner that the formation of lakes in the presence or in theabsence of substrata or with simultaneous formation of substrata, takesplace in accordance with one of the following methods. From azo-dyeswithout sulfogroup, insoluble lakes are prepared in such manner that thecombination of the diaz'ocompound with the other components, forinstance of paranitranilin with beta-naphthol takes place in thepresence or absence of fatty acids, colloids etc. When-azo-colors withone or more sulfo-groups are used, the lake is prepared in such mannerthat easily soluble sodium salts, such as for instance orange II B,Ponceau 2 R etc. are dissolved boiling and then precipitated with metalsalts. Azo-colors of the above class which are soluble with diflicultyeven in the form of their sodium salts, such as for instance lithol andlake red, are treated boiling or at an ordinary temperature and. whilein suspension with a solution of metal salts until the decomposition hastaken place. Therefore in the case of azo-colors with sulfogroups alwaysa double reaction takes place.

This invention relates to a process for manufacturing insolubleazo-lakcs from azo dyes with one or more sulfo-groups in which the metalsalts are obtained not by double decomposition, but the formation of thedye and of the lake takes place in one operation, which begins directwithmetal salts of the sulfo-acidh or is carried on in such manner thatat the 'end of the combination, all the sulfo-groups are bound tometals. It is true that previously a process has been described in whichthe inventor has tried to combine in one operation the formation of anazodye and the precipitation of a lake, but in that case there is stillthe double decomposition. It was thought that the conditions for thereaction must be chosen in such manner as to form first the alkali saltwhich immediately afterwards enters into reaction with the metal salt.Moreover while in such a Specification of Letters Patent.

Patented Jan. 19, 1909.

process it is only a question of azo-colors with sulfo-grou vvs in thesecond component, the process according to this invention can be appliedalso to azo-colors with sulfogroups in the first component, or even inboth com onents. The process, has therefore, the following advantages.

1. As according to the new process the formation of sodium salt of theazodye is done away with, the soda required for forming the sodium salt,is economized, and also the hydrochloric acid required for convertingmetal carbonates into metal chlorids, moreover the manufacture isreduced by one operation.

2. In the prior process hereinbefore referred to common salt is obtainedas impurity: (a) during the diazotizing, (b) during the combination, (0)owing to the reaction of the sodium salt. of the azo-dye with metalchlorids. According to this process, as the reaction of the sodium saltis completely done away with, thelake is obtained. from the beginning ina much purer form. Moreover, the formation of a common salt can be stillfurther avoided by carrying on the diazotizing with hydrochloric acidwhich is subsequently utilized as a substratum by means of a bariumcarbonate. The lakes need, therefore, very little washing.

3. The lakes are obtained direct with the full depth of their color,they require, therefore, to be ground only for a short time, while lakesprepared from azo-colors soluble with dilliculty, such as lithol-red andlakercd, had to be ground for several hours. 'lherofore in case wherethe corresponding dye itself or the corrcspmiding substratum, as forinstance minium, become duller when subjected to long grinding thisprocess is of a considerable advantage for obtaining clear shades. Y

4. At the double decomposition of sodium salts with metal salts. dye notprecipitated is often mechanically carried down. If such a lake thensubsmplcutly ground the solublc salt of sodium of the azo-dve is againrendered free. The lake is then no longer waterproof, which is oftennoticeable in. printing and lithographic ink, Naturally the abovedrawback is avoided by the process according to this ii'ivciniou.

5. According to the process of this application, not only the old shadescan be obtained which are produced by the reaction of the sodium saltswith metal salts, but

quite considerable changes of shade are brought about by tricks oradditions during the combination, and therefore lakes can be produced ofsuch fast color as was hitherto absolutely impossible to produce. Assuch additions oleic acid, palmitic acid, stearic acid, Turkey red oil,glue, gum,v albumin,

tragacanth, starch, glycerin'c'ould be used.

6. Dyes with two or more sulfo-groups which hitherto could ,notbeprecipitated, or only with great difiiculty, as the sodium of theirsalts could be only partiall replaced by other metals, are rendered use1 for the "lake industry, as of course the binding of? all thesulfo-grou s to metals can be obtained.

-7. It is furt er possible to reduce double in one molesulfo-groups ofone component to barium, and o the other component to calcium. Of

course, the process can also be carried out insuch way that after thecombination, the sulfo-groups of one component are already bound to ametal, while the sulfa-groups of the second com onent which are bound toan alkali, are 0 y then treated with solutions of metal salts. Ratherthe operation can be carried on in such manner that in the caie ofsullfoeigids with several bosulfo u t esing e sn 0- oupscan un t d diil' drent metals, for i stance, in the case of disulfo-acid, onesulfa-group is bound to barium, and the other to copper.

8. In dyes containing naphth'ol in the second com nent, soda-lyecan bereplaced by other so vents, for instance, Turkey red 0' soaps, bariumand calcium hydroxid.

9. As combination agents, could be used in the process 'accordin to thisinvention, cheap carbonates an hydroxide such as witherit, chalk, limeetc.

Compared to the old process, the process according to this invention istherefore considerably cheaper, better and sim ler.

A few examples will'explain t 'e same.

a) sul a-cam a the First am mnt.

Example I. 17.3 kg. of sulfanilic acid, 10

of carbonate of barium are converted boiling into sulfam'late of barium.The solution is mixed with 25 kg. of h .drochloric acid'of 19 B. cooledto 0 an diazotized with 7 k of sodium nitrite in liters of water. fterthe free hydrochloric acid has been neutralized by the addition ofcarbonate of barium, the diazo-com oundis introduced into a solution of14.5 g. naphthol, 4; kg. of acid and 15 kg. of Turkey red oil of 50%.After'the combination has been converted, 1200 kg. of a paste of hydrateoi alumina are added. The lake produced, which can be used as printingand lithographic is considerably more red than when pre ared withoutTurkey red dil. Y Examp e 2. 22.3 kgs. of naphthyl-aminsulfo-acid 2.8are dissolved boiling with 5 k of chalk, and 25 kg. of hydrochloric acido 19 B. are added. The free sulfo-acid again separated is thendiazotized'at about 20 with a solution of? kg. nitrite. After havingneutralized the excess of hydrochloric acid with chalk, the beautifulyellow diazo-compound is introduced into the following mixture. 14.5 kg.'beta-naphthol in powder are mixed with water, then milk of lime,prepared from 2.8 kg. of caustic lime, is added, and also 500 kg. ofheavy spar are added. After having introduced the diazo-compound,further quantities of milk of lime are added until, after several hoursstirring, there is a slightly alkaline reaction. Then the lake becomesof a beautiful cinnabar red which can be used as oil paint, whichadheres" well to the surface to e painted, and is subjected to furthertreatment in the usual manner.

(b) Sulfa-Group in the Second Gomponent.

Exam le 3. 10.7 kg. toluidin and 25 kg. hydroc in water, cooled with iceand diazotized with a solution of 7 kg. of nitrite. After thediazocompound has been mixed with cold solution of 70 k of crystallizedGlauber salt, it is intro uced into the followingmixturez-32A kg. of nahthoLsulfoacid 1.5 are converted into a s t of barium with theequivalent quantity of carbonate of barium. To this is added a solutionof 50 kg. of barium chlorid, then 15 kg. of barium carbonate and 300 kg.of orange minium are added. If, after several hours of stirring, thereis still a'samll quantity of diazocompound, as much milk of lime isadded as necessary to cause the last traces of the diam-compound tocombine. The cirmabar imitation thus prepared has at once its full dc thof color, so that it need be ground 0 y for a short time.

Example 4. 30.4 kg. of naphthol-di-sulfo form of paste as paint for wallpapers.

(0) Sulfa-Groupain Both Oomponents.

Example 5. 30.3 kg. of naphthyl-amin-dioric acid of 19 B. are dissolvedsulfo -acid 2.3. 6, and 10 k of chalk are dissolved boiling. 25 kg.hydrochloric acid of 19 Be. are added, and the whole is diazotized at 20with the solution of 7 kg. nitrite.

The yellow diazo-compound is introduced into the following solution:30.4 kg. naphthol-di-sulfo-acid 2.3.6 are dissolved boiling,

with kg. of chalk. To that are added 200 kg. of kaolin and 200 kg. ofheavy spar, and then milk of lime is slowly added until the formation ofdye stuff is completed.

Example 6. The operation is carried on in the same way as in Example 5,with the difference that 30.4 kg. of naphthol-di-sulfoacid 2.3.6. areconverted into salt of barium in the usual manner. The lake produced inwhich the two-sulfogroups are combined with barium and two to calcium isconsiderably more blue than the previous one.

Having thus'fully described the na ure of my invention, what I desire tosecureby Letters Patent of the United States is:-'

1. A process of making azo-lakes which consists in formin the dyesimultaneously with the precipitatlon of the lake in the absence ofalkali so that the sulfo-groups are all united directly to metallicconstituents. 2. A process of making azo-lakes' which consists informing the dye simultaneously with the precipitation of the lake in theabsence of alkali so that the sulfo-groups are all united directly tometallic constituents,

